Acylation of diethyl (ethoxycarbonylfuryl)methanephosphonates under the conditions of claisen reaction

O,O-Diethyl (ethoxycarbonylfuryl)methanephosphonates are formylated with ethyl formate in the presence of sodium foil at the methylene group adjacent to phosphorus atom to form sodium salts of phosphonoacetic aldehyde. When the substituents in the furan ring are remote from one another, and also in the case of 3, 4-disubstituted isomer these salts in DMSO solution exist in the carbanion form. Anions of salts of (2-ethoxycarbonylfur-3-yl)phosphonoacetic aldehyde and the isomer with the reversed location of substituents in DMSO solution take part in the dynamic equilibrium between the carbanion and the enolate form. The alkylation of all salts obtained with allyl bromide and dimethyl sulfate proceeds exclusively at the oxygen to form a mixture of Z- and E-isomers of phosphorylated vinyl ethers.     

Reaction between chromium(III) oxide and oxygen in the presence of sodium carbonate

The large scale manufacture of sodium chromate is carried out by heating finely ground chromite ore mixed with sodium carbonate and lime in air. The essential reaction leading to the formation of sodium chromate is $$2Cr_2 O_3 + 4 Na_2 CO_3 + 3 O_2 \xrightarrow{{\Delta {\rm H}_{R^0 } }}4Na_2 CrO_4 + CO_2 $$      

Synthesis and Wittig Reaction of Formylated (Trifluoromethylfuryl)methanephosphonates

Methods of synthesis of 4-functionalyzed (5-trifluoromethylfur-2-yl)methanephosphonates and (5-methyl-2-trifluoromethylfur-3-yl)methanephosphonate are developed. Their formylation with ethyl formate in the presence of sodium foil is studied. Spectral characteristics of tautomers of obtained derivatives of phosphonoacetic aldehyde are evaluated. It is shown that interaction of obtained formyl derivatives with ethoxycarbonylmethylenetriphenylphosphorane regardless of the structure of the furan fragment leads to 4-furylsubstituted alkyl 4-(diethoxyphosphoryl)but-3-enoate, the abnormal product of Wittig reaction.     

Reaction of diethyl (phthalimidoacetyl)malonate with hydroxylamine

The reaction of diethyl (phthalimidoacetyl)malonate with hydroxylamine was investigated. Depending upon the reaction conditions, N-phthaloylglycinehydroxamic acid ( 2 ) and the cyclized product, 4-ethoxycarbonyl-5-hydroxy-3-(phthalimidomethyl)isoxazole ( 4 ), were obtained.     

Reactions of alkoxy(chloromethyl)methylsilanes with sodium diethyl phosphate and with sodium dimethylphosphinate

Summary The reactions of alkoxy(chloromethyl)methylsilanes with sodium diethyl phosphate and with sodium dimethylphosphinate provide a method for the preparation of some silicon-phosphorus organic compounds containing an Si-C-O-P linkage and functional groups attached to the silicon atom.     

Design,synthesis, crystal structure and bioactivity evaluation of novel diethyl (arylfuranyl)(arylpyrazolylamino)methanephosphonates

A series of novel arylpyrazole derivatives containing aminomethanephosphonate and phenylfuran moieties were designed, synthesized and characterized by ¹H NMR, ³¹P NMR and IR spectroscopy and elemental analyses. The single crystal structure of diethyl [5-(4-chlorophenyl)furan-2-yl][3-cyano-1-(2,3,4-trifluorophenyl)-1H-pyrazol-5-ylamino]methanephosphonate (4l) was determined by X-ray diffraction. Preliminary bioassays showed that these phosphonates exhibit satisfactory insecticidal activities against Culexpipiens and Musca domestica at 0.1%. In particular, compound 4l exhibited a most promising KT50 value, which is superior to that of Dextraltetramethrin® and similar to Prallehtrin®. The structure-activity relationship was also preliminarily investigated.     

Reaction of dibromoadamantanes with glycols in the presence of sodium glycolate

1,3-Dibromoadamantanes reacted with glycols in the presence of sodium glycolate to give novel unsaturated bicyclo[3.3.1]nonane derivatives and 1,3-disubstituted adamantanes.     

2-(1-Chloroalkyl)furans in the reaction with sodium diethyl phosphite

2-(1-Chloroethyl) and 2-(1-chloro-2-methylpropyl)furans react with sodium diethyl phosphite to give two products, 2-(1-diethoxyphosphorylmethyl)furan and 2-alkyl-5-(diethoxyphosphoryloxy)furan. The fraction of the latter product increases with increasing size of the alkyl radical. 2-Methyl substitution in the substrate completely suppresses phosphate formation. 2-(1-Chloroethyl)-5-(2-methylpropyl)furan under the action of sodium diethyl phosphite eliminates hydrogen chloride to give the corresponding alkene.     

α-氰基苄基碳负离子钠盐与碳酸二乙酯的单电子转移反应动力学和机理

测定了α-氰基苄基碳负离子钠盐与碳酸二乙酯缩合反应产物的结构及其分布,反应中间体的EPR谱,反应过程中产物和溶剂的CIDNP效应和反应动力学,为这一缩合反应提出了单电子转移-负离子自由基分解-自由基偶合的非链式自由基机理     

Reaction of sodium N-benzylideneglycinate with dialkyl chlorophosphites in the presence of water

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Reaction of sodium octahydrotriborate with biscyclopentadienylzirconium(IV) dichloride

Conclusions Sodium octahydrotriborate reacts with Cp₂ZrCl₂ in THF, ether or CH₂Cl₂ to give Cp₂ZrClBH₄.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 417–419, February, 1984.     

Crystallization and aggregation behaviors of calcium carbonate in the presence of poly(vinylpyrrolidone) and sodium dodecyl sulfate

An anionic surfactant interacts strongly with a polymer molecule to form a self-assembled structure, due to the attractive force of the hydrophobic association and electrostatic repulsion. In this crystallization medium, the surfactant-stabilized inorganic particles adsorbed on the polymer chains, as well as the bridging effect of polymer molecules, controlled the aggregation behavior of colloidal particles. In this presentation, the spontaneous precipitation of calcium carbonate (CaCO3) was conducted from the aqueous systems containing a water-soluble polymer (poly(vinylpyrrolidone), PVP) and an anionic surfactant (sodium dodecyl sulfate, SDS). When the SDS concentrations were lower than the onset of interaction between PVP and SDS, the precipitated CaCO3 crystals were typically hexahedron-shaped calcite; the increasing SDS concentration caused the morphologies of CaCO3 aggregates to change from the flower-shaped calcite to hollow spherical calcite, then to solid spherical vaterite. These results indicate that the self-organized configurations of the polymer/surfactant supramolecules dominate the morphologies of CaCO3 aggregates, implying that this simple and versatile method expands the morphological investigation of the mineralization process.     

Reaction of diethyl acetonedicarboxylate with nitrosyl chloride

The reaction of diethyl acetonedicarboxylate with greater than two equivalents of nitrosyl chloride or the reaction of diethyl isonitrosoacetonedicarboxylate with one equivalent of nitrosyl chloride gave diethyl 4-hydroxyisoxazole-3,5-dicarboxylate in quantitative yield. Mechanistic possibilities are discussed.     

Reaction of α-ethoxyarolein with diethyl malonate

The reaction of α-ethoxyacrolein with diethyl malonate in the presence of EtONa, lithium diisopropylamide, or the Na₂CO₃−benzene−Et₃(PhCH₂)NCl catalytic system proceeds as the Michael addition. In the presence of an equimolar amount of triethylamine, selective 1,2-addition followed by dehydration of the 1,2-adduct occurs. Owing to the strong +M effect of the EtO group, α-ethoxyacrolein is a substantially less active Michael acceptor than acrolein. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 12, pp. 2508–2510, December, 1998.